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Cycloheptatrienyl (tropyl) molecules are representative non‐alternant hydrocarbons that offer interesting chemistry because of their unique structures and properties. However, there have been a limited number of polycyclic aromatic tropyl cations and radicals reported in the literature. Herein, we report the synthesis of a series of azahomocorannulene derivatives, where the key reactions are a 1,3‐dipolar cycloaddition of polycyclic aromatic azomethine ylides with dibenzotropone and a subsequent palladium‐catalyzed cyclization. X‐ray diffraction analysis revealed that the obtained azahomocorannulenyl cation and radical adopt planar structures and exhibit unique packing structures. Their electronic and optical properties were investigated experimentally and theoretically to reveal their aromatic character. [ABSTRACT FROM AUTHOR]

An autoionization of germanium dichloride/dioxane complex with an imino-N-heterocyclic carbene ligand ( L) afforded a novel germyliumylidene ion, [( L)GeCl]+[GeCl3]−, which was fully characterized. Reduction of the germyliumylidene ion with potassium graphite produced a cyclic species [( L)Ge], which can be viewed as both a Ge0 species and a mesoionic germylene. X-ray diffraction analysis and computational studies revealed one of the lone pairs on the Ge atom is involved in the π system on the GeC2N2 five-membered ring. It was also confirmed that the nucleophilic behavior of [( L)Ge] as a two lone-pair donor. [ABSTRACT FROM AUTHOR]